Pesticidal nicotine alkaloid salts of dithiocarbazic or dithiocarbamic acids



United States Patent "Ice WM Patented Jan. 16, 1968 ABSTRACT OF THE DISCLOSURE Compounds useful as fungicide, bactericide, antivirus agent, insecticidal agent, nematicide and herbicide comprising nicotinic alkaloid salts of (a) polythiocarbamic acid, N-dialkyl dithiocarbamic acid, N mono-alkyl-dithiocarbamic acid, N-mono-phenyl-dithiocarbamic acid or dithiocarbazic acid, or mixtures thereof, wherein each alkyl group has 1 to 3 carbon atoms; with (b) a nicotinic alkaloid selected from the group consisting of nicotine, neonicotine and anabasine.

This application is a continuation-in-part of our copending application Ser. No. 347,045, filed Feb. 24, 1964, now abandoned.

An object of this invention is to provide new compositions which have fungicidal, bactericidal, antivirus, ovicidal, insecticidal, nematicidal and herbicidal activities, which give plants resistance to disease, and which have an accelerating effect on metabolism, and which also have pesticidal action on fishes.

Another object of this invention is to provide useful pesticides containing a new chemical compound as an active ingredient.

The pesticides of the present invention are characterized by containing, as active ingredient, at least one of nicotinic alkaloid salt selected from the group consisting of dithiocarbamic acid, dithiocarbazic acid such as polydithiocarbarnic acid exemplified by alkylene bisdithiocarbamic acid and di-lower alkyl dithiocarbamic acid exemplified by dimehyl dithiocarbamic acid and mono-lower alkyl dithiocarbamic acid exemplified by mono-methyl dithiocarbamic acid and dithiocarbazic acid. When needed, other salts of the above-mentioned dithiocarbamic acid and/or carbazic acid excepting alkaloid salt, the other alkaloid salts excepting abovementioned acid salt or free alkaloid, or other kinds of active ingredient may be added.

First of all the active components of the agent of this invention shall be explained. All of the above-mentioned active components are new compounds. Suitable dithiocarbamic acid of this invention are as follows.

Among useful polydithiocarbamic acid, there are alkylene bisdithiocarbamate such as ethylene-bis-dithiocarbamate, polyalkylene polydithiocarbamate derived from polyalkylene polyarnide, for example, diethylenetriaminebis-dithiocarbamate and/or diethylenetriamine-tris-dithiocarbamate obtained from diethylenetriamine or polydithiocarbamate derived from triethylenetetramine and cyclic tn'methylenetriamine, that is, methylenedithiocarbamate, alkyl methylenedithiocarbamate, these compounds indicated by following formulas:

and the compound indicated by following formula:

and

or its polymer, polydithiocarbamate containing aromatic nucleus such as phenylene bisdithiocarbamate and xylene bisdithiocarbamate and heterocyclic dithiocarbamate such as piperazine bisdithiocarbamate. Monomethyl dithiocarbamate is a typical example of mono-substituted dithiocarbamate. In this group, there are monoalkyl dithiocarbamate such as monoethyl and monopropyl dithiocarba mate and aromatic mono-substituted dithiocarbamate such as phenyl dithiocarbamate. Dithiocarbazic acid derived from hydrazine and phenyl dithiocarbazic acid are the typical of dithiocarbazate. As nicotinic alkaloid, nicotine is the typical example, and it has the following formula w I l on (i-on (11H:

\CH CH2-CH:

As tflll'l'lhel nicotinic alkaloids, there are neonicotine, anabasine, and the like. Neonicotine and anabasine have the same structure as shown in the following:

032 I Z CH Anabasine is contained in a weed, belonging to the genus of sugar-beet (Anabasis aphylla), and optically active, while neonicotine is optically inactive. Commercially they are sold as neonicotine as contaminated with dipyridyl and pyridyl piperidine, etc., and both of them may be employed as the salt component of the agents of the present invention.

The activity and characteristic properties of the compositions of the present invention will be explained as follows. The compositions of this invention exhibit the high bactericidal, fungidical, antiviral, insecticidal, nematicidal, herbicidal, and ovicidal activities at the same time, and moreover, give the treated plants the disease resistance.

Strongly basic alkaloids such as nicotine, neonicotine, anabasine and dithiocarbamic acid produce stable salts and can be stored for a long period. The usual insecticides, particularly chemically synthesized insecticides, sometimes have strong harmful effects (phytotoxicity) against host plants applied with them, and therefore careful consideration is needed for application of them. Nicotine anabasine itself is a component derived from some plants, and has been evaluated from old time as a safe insecticide with the lowest phytotoxicity. Water-soluble dithiocarbamate shows a same shock to plants. Therefore, in general, it is used in the form of insoluble salt such as zinc salt, and its fungicidal action is practically exhibited through its slight solubility. Out of water-soluble salts, ammonium salt is most unique at the point of giving the least shock to plants and showing pesticidal action after absorbed into plants. Amine salts show almost the same characteristics of ammonium salts. Ammonium salt and amine salt have a very high activity and therefore can be applied in lower concentration. And then, they are very economical since they show marked activity even in low concentration. In the case when high molecular amine salt such as nicotine, neonicotine anabasine is used, this shock effect becomes remarkably weakened, that is, it has no phytotoxicity. Moreover, the strong pesticidal effect of amine salt is retained; the chemicals of this invention are extremely useful. The characteristic of this chemical composition is to generate various activities at the same time. Thus, nicotine salts have strong insecticidal activity in addition to all kinds of the above-mentioned activities of dithiocarbamate and dithiocarbazate.

The research and development of the chemical compositions which show the many activities at the same time is now a matter of urgent necessity. The problems concerning agricultural chemicals will be discussed below.

The damages caused by fungi, bacteria, virus, nematodes, harmful insects and the like have been considered to occur separately, and therefore the pesticide of the single purpose has been considered separately for each damage. However, such a concept is not true, since fungi, bacteria and virus infect plants at the same time and make disease-complex develop. Soil-nematode also gives the damages in cooperation at the same time with bacteria and fungi. Virus, bacteria and fungi are carried by the harmful insects, and damages caused by them become spread. The pesticidal composition of this invention is most suitable for the purpose under such consideration. By the application of these chemicals, bactericidal, antiviral and nematocidal activities due to dithiocarbamate are synchronized with insecticidal activity due to nicotine, neonicotine, anabasine. The interesting eflect of this composition is prevention and expulsion of virosis, virus-fungibacteria-mixed infection and insect pests. It seems that owing to fungicidal, bactericidal, and antiviral effects and strengthening effect to plant activity of dithiocarbamate, cooperated with preventing effect to insectvectors of nicotine, neonicotine, anabasine, this composition exhibit such superiority.

Nicotine salt of monomethyl-dithiocarbamic acid can be quoted as chemical composition which shows an interesting etfect. This salt is decomposable in the soil to form methylisothiocyanate, which diffuses into soil in a form of gas and shows a strong bactericidal, insecticidal, nematocidal and herbicidal activities. As to the nicotine salt, it appeared that fumigative nicotine also diffused into soil and showed splendid ovicidal activity and strong effect against molluscous insects and larval, and thus it exhibited combined eifect.

And, the nicotine salt, neonicotine salt, anabasine salt of dithiocarbamic acid has specific character as follows. Ammonium salt and amine salt of dithiocarbamic acid are stable when pH of the system is more than 7 and can be stored for a long period. Nicotine salt, neonicotine salt, anabasine salt have the same properties as other amine salt and ammonium salts. Fortunately, nicotine, neonicotine, anabasine have better activity under this condition. Furthermore, nicotine, neonicotine, anabasine show stronger activity at combined state than nicotine, neonicotine, anabasine alone. This fact seems to be produced by the synergistic elfects which is the same as wellknown effect by potassium ion. In order to maintain the stability and activity of this chemical composition according to the present invention, it is preferable to add an adequate pH adjuster.

The carrier to be added to the active ingredients of the agents of the present invention is normally water, when.

they are water-soluble, while organic solvents such as alcohols, for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, amylalcohol, ethylene glycol, glycerin; ketones, for example, acetone and methylethylketone; dimethylformamide and dimethylsulfoxide, etc., and solid carriers such as talc and clay may also be employed.

In manufacturing said chemical composition with said alkaloid salts of dithiocarbamic acids, it is able to be combined for not only such water-soluble salts of dithiocarbamic acids as general salts, ammonium salts, amine salts, sodium salts, potassium salts, magnesium salts, and quarternary ammonium salts, but also such water-insoluble salts and derivatives etc. as zinc salts, manganese salts, iron salts, nickel salts, copper salts, salts of more than two kinds of metals, thiurams, sulfenirnide, metal-containing thiuram (methiram) compounds, complex salts of more than two metals and the like. While, free alkaloids and alkaloid salts can be combined with above-mentioned alkaloid salts of dithiocarbamic acids. This fact is very important in practical use. Namely, when one chemical composition has to have more than two kinds of action, a certain dilution-rate profitable for one activity is often unsuitable for the other activity. With accordance to the above-mentioned way, it is possible to decide the amount of these compounds in order to be suitable for both activities.

In general the present new compounds are prepared as follows:

Into a 4-necked flask, there are introduced 1-1.2 equivalent (2-2.4 equivalents in the case of diamine) of carbon bisulfide and 250-550 g. of water; 1 equivalent of amine is added dropwise from a tap funnel with agitation; at the reaction temperature from 40 to 45 C. the free acids are synthesized. At the later term of the synthesis of the free acids, 1 equivalent of nicotine extract solution) is added. It is cooled after one-hour agitation at 4045 C. Excess of carbon bisulfide expelled off at 45 -50 C. After cooling, its pH is adjusted to 8.8-9.0 with gaseous ammonia.

EXAMPLARS For the purpose of illustration, methods of synthesis and analysis for a few compounds are shown in the following.

EXAMPLE 1.SYNTHESIS OF NICOTINE ETHYL- ENE-BISDITHIOCARBAMATE Into a 4-necked flask, there are introduced 167 g. (2.2 mols) of carbon bisulfide and 540 g. of water; 106 g. (56%, 1 mol) of ethylenediamine is added dropwise from a tap funnel with agitation; at the reaction temperature from 40 to 45 C., there are provided an orange-yellow liquid containing white precipitates. Upon adding 341 g. of nicotine extract (95%, 1 mol) dropwise into the liquid, it turns to a brownish black, clear liquid. It is cooled after one hour agitation at 40-45 C., excess of carbon bisulfide is expelled off at 4550 C. After cooling, its pH turns to about 7.8, therefore it is adjusted to 8.8-9.0 with gaseous ammonia. 1000 ml. of 45% product is obtained.

Method 0 analysis (a) Method of analysis for active ingredient.-About 7.6 g. of sample is precisely weighed (W) and introduced into a 250 ml. measuring flask, and diluted with deionized water up to the marked line. After mixing thoroughly, 25 ml. of this solution is introduced into a decomposition flask with a whole pipette. The first absorption tube is filled with 25 ml. of 10% lead acetate solution, the second absorption tube with 25 ml. of 2 N methanolic potassium hydroxide solution. With both tubes being watercooled and suction being regulated, 50 ml. of hot 1.1 N sulfuric acid from the top of the center tube and the content is intensely heated to be decomposed. Upon terminating heating after 1% hour period, methanolic potassium hydroxide solution is washed out with deionized water into a 500 ml. conical beaker and neutralized with 30% acetic acid employing phenolphthalein as an indicator, thence titrated With 5 N iodine solution, employing starch as an indicator.

Percent of active ingredient=iflv gflq;

(b) Method of analysis for nicotine portion-A sample containing about 2 g. of nicotine is precisely Weighed 1 into a 500 ml. round-bottomed distillation flask, and 20 ml. of water, g. of NaCl and 10 ml. of natrium hydroxide (30%) are added, zeolite being introduced thereto, also. As a receiver, 1 liter measuring flask is employed, to which 10 ml. of diluted hydrochloric acid has been previously introduced, the tip point of cooling pipe being kept submerged in the solution only a bit. Upon connecting the distillation flask and the cooling pipe, steam distillation is started. Upon the start of distillation, the distillation flask is heated and the volume of the liquid is regulated. Distillation is continued and 1-2 ml. of distillate is taken into a test tube to test for cloud or turbidity by adding a drop of (1+4) diluted hydrochloric acid silicotungstic acid solution and a drop of 1+4) diluted hydrochloric acid. After cloud has ceased to appear, the tip of cooling pipe is pulled out of the distillate and washed with deionized water, the washings being combined with the distillate and the distillation being terminated. The residue in the distillation flask is certified for its alkalinity by adding phenolphthalein indicator. A portion of the distillate is taken to test for its acidity by adding methyl orange indicator, and 100 ml. of the distillate is transferred into a beaker with whole pipette, to which 3 ml. of 1+4) diluted hydrochloric acid is added, then While heating, silicotungstic acid solution being added. In order to grow crystals larger, heating with agitation and cooling are repeated several times, thereupon it is allowed to stand overnight at room temperature.

The precipitate is filtered with a quantitative filter paper and thoroughly washed with (1+4) diluted hydrochloric acid. After drying, the precipitate is transferred together with the filter paper into a crucible, the Weight of which has been known, and ignited to constant Weight.

Calculation:

114.0Xresidue sample g.) NICOTINE DlME'lHYL-DITHIOCARBAMATE Method 0 synthesis 84 g. (1.1 mols) of carbon bisulfide and 200 g. of water are introduced into a 4-necked flask, and 113 g. (40%, 1 mol) of diethylamine is added dropwise thereto with agitation from a tap funnel. After agitation of one hour since the completion of the addition, 170 g. of nicotine extract (95%, 1 mol) is added dropwise and the solution turns to a brownish black, clear liquid. Upon cooling after agitating for one hour at 4045 G, excess of carbon bisulfide is driven ofi" at 45 50 C. As the pH turns to about 7.8 after cooling, it is adjusted to 8.8-9.0 with gaseous ammonia. 500 ml. of about 47% product is obtained.

Percent of nicotine= Method of analysis (a) Method of analysis for active ingredient.About 1 Sample is stored in a dropping bottle and weighed previously, A certain quantity of the sample to be required is introduced to a distillation flask. and the weight difference between before and after the transfer is determined as the weight of sample taken (2.).

120 g. of silicotungstic acid (4HgO-S1O2-12WO3-22H2O) is dissolved in water and the solution is diluted to make one litre, There are several classes of silicot'ungstic acids. and be cause those having the compositions of 4H2O-Sl 02-10WO a 3H2O and 4H20SiO2'12WO32-H50, form no crystalline precipitate, they should not be used.

Wnshing is conducted until no cloud appears upon adding a few drops of nicotine distillate to 23 ml. of fresh washings taken in a test tube.

6 7.6 g. of sample is precisely weighed and introduced into a 250 ml. measuring flask, and then diluted with deionized water up to the marked line. After mixing thoroughly, 25 ml. of this solution is introduced to a 125 ml. decomposition flask, and 25 ml. of 10% lead acetate solution is added to the first absorption tube and 25 ml. of 2 N methanolic potassium hydroxide solution to the second absorption tube, both of the tubes being water-cooled. Suction is regulated and from the top of the center tube, 50 ml. of 1.1 N hot sulfuric acid is introduced and the content is intensely heated to be decomposed. After a period of 1% hours, heating is terminated and at once the methanolic potassium hydroxide solution is washed out into a 500 ml. conical beaker with deionized water. After neutralizing with 30% acetic acid employing phenolphthalein as an indicator, titration is conducted with 1/ 10 N iodine solution, employing starch as an indicator.

Percent of active mgredrent=W (b) Meth d of analysis for nicotine portion-The same as in the case of nicotine ethylene-bis-dithiocarbamate.

NICOTINE DITHIOCARBAZATE Method of synthesis 84 g. of carbon bisulfide (1.1 mols) and 300 g. of Water are introduced into a 4-necked flask and agitated. From a tap funnel, 100 g. of hydrazine hydrate (50%, 1 mol) is added dropwise and agitation for one hour at about 40 C. is conducted. Upon adding 170 g. of nicotine extract 1 mol), the solution turns to a brownish black, clear liquid. Excess of carbon bisulfide is driven oil at 4550 C. and upon adjusting pH to 9.00, 600 ml. of 40% product is obtained.

Method of analysis (a) Method of analysis for active ingredient.-The same as in the case of nicotine ethylene-bis-dithiocarbamate, but the calculation may be done as follows:

Percent of active ingredient=m (17) Method of analysis for nicotine portion.The same as in the case of nicotine ethylene-bis-dithiocarbamate.

NICOTINE MONOMETHYL-DITHIOCARBAMATE Method of synthesis Into a 4-necked flask, there are introduced 84 g. (1.1 mol) of carbon bisulfide and 200 g. of water; g. (30%, 1 mol) of monomethylamine is added dropwise from a tap funnel with agitation. After agitation of one hour since the completion of the addition, g. of nicotine extract (95%, 1 mol) is added dropwise and the solution turns to a brownish black, clear liquid. Upon cooling after agitating for one hour at 4045 C., excess of carbon bisulfide is driven ofl at 4550 C. The pH is adjusted to 8.8-9.0 with gaseous ammonia. 500 ml. of about 48% product is obtained.

mate of the revised specification, but the calculation may be done as follows:

Percent of active 1ngred1ent=W (1)) Method of analysis for nicotine portion.The same as in the case of nicotine ethylene-bis-dithiocarbamate.

NICOTINE DIETHYLENETRIAMINE-TRISDITHIO'- CARBAMATE Method of synthesis Into a 4-necked flask, there are introduced 252 g. (3.3 mols) of carbon bisulfide and 680 g. of water; 206 g. (50%, 1 mol) of diethylenetriamine is added dropwise from a tap funnel with agitation. After agitation of one hour since the completion of the addition, 510 g. (95%, 3 mol) of nicotine extract is added dropwise and the solution turns to a brownish black, clear liquid. Upon cooling after agitating for one hour at 40-45 C., excess of carbon bisulfide is expelled oil at 45-50 C. The pH is adjusted to 8.8-9.0 with gaseous ammonia. 1550 ml. of about 49% product is obtained.

Method analysis (a) Method of analysis for active ingredient.The same as in the case of nicotine ethylene-bis-dithiocarbamate, but the calculation may be done as follows:

20111.) X F12 X 27. 13 Percent of active ingredient Sample (g.

(b) Method of analysis for nicotine portion-The same as in the case of nicotine ethylene-bisdithiocarbamate.

' NICOTINE PHENYLEN'E-BISDITHIOCARBAMATE Method 0] synthesis Into a 4-necked flask, there are introduced 168 g. (2.2 mol) of carbon bisulfide and 600 g. of water; 108 g. (1 mol) of solid phenylene diamine is added slowly with agitation. After agitation of one hour since the completion of the addition, 341 g. of nicotine extract (95%, 2

(a) Method of analysis for active ingredient.-The same as in the case of nicotine ethylene-bisdithiocarbamate, but the calculation may be done as follows:

Percent of active ingredient=.-

sample (g.)

(b) Method of analysis for nicotine p0rtion-.-The same as the case of nicotine ethylene-bisdithiocarbamate.

NICOTINE PHENYL-DITHIOCARBAMATE Method of synthesis Into a 4-necked flask, there are introduced 84 g. (1.1 mol) of carbon bisulfide and 250 g. of water; 93 g. (1 mol) of aniline is added dropwise with agitation. After agitation of one hour since the completion of the addition, 170 g. of nicotine extract (95%, 1 mol) is added dropwise and the solution turns to a brownish black, clear liquid. Upon cooling after agitating for one hour at 40-45 C., excess of carbon bisulfide is expelled oif at -50 C. The pH is adjusted to 8.8-9.0 with gaseous ammonia. 470 ml. of about 47% product is obtained.

Method of analysis (a) Method of analysis for active ingredient-The same as in the case of nicotine ethylene-bisdithiocarbamate, but the calculation may be done as follows:

Percent of active ingredient sample (g.)

(b) Method of analysis for nicotine portion.-The same as in the case of nicotine ethylene-bisdithiocarbamate.

, 8 NICOTINE PIPERAZINE-BISDITHIOCARBAMATE Method of synthesis Into a 4-necked flask, there are introduced 167 g. (2.2 g

Method of analysis (a) Method of analysis for active ingredient.The same as in the case of nicotine ethylene-bisdithiocarbamate, but the calculationmay be done as follows:

Percent of active ingredient sample (g.)

(b) Method of analysis for nicotine p0rtion.The same as in the case of nicotine ethylene-bisdithiocarbamate.

NEONICOTINE ETHYLENE-BIS- DITHIOCARBAMATE Method of synthesis Into a 4-necked flask, there are introduced 167 g. (2.2 mol) of carbon bisulfide and 50 g. of water; 106 g. (56%, 1 mol) of ethylenediamine is added dropwise from a tap funnel with agitation. After agitation of one hour since the completion of the addition, 1080 g. of neonicotine solution (30%, 2 mol) is added dropwise. Upon cooling after agitating for one hour at 40-45 C., excess of carbon bisulfide is expelled oil? at 45 -50 C. The pH is adjusted to 8.8-9.0 with gaseous ammonia. 1380 ml. of about 38% product is obtained.

Method of analysis for active ingredient The same as in the case of nicotine ethylene-bis dithiocarbamate.

NEONICOTINE DIMETHYL-DITHIOCABAMATE Method of synthesis 84 g. (1.1 mol) of carbon bisulfide and 50 g. of Water are introduced into a 4-necked flask and 113 g. (40%, 1 mol) of dimethylamine is added dropwise thereto with agitation from a tap funnel. After agitation of one hour since the completion of the addition, 540 g. of neonicotine solution (30%, 1 mol) is added dropwise. Upon cooling after agitating for one hour at 40-45 C., excess of carbon bisulfide is expelled ofl at 45-50 C. The pH is adjusted to 8.8-9.0 with gaseous ammonia; 550 ml. of about 32% product is obtained.

Method of analysis for active ingredient The same as in the case of nicotine dimethyl-dithiocarbamate.

NEONICOTINE DITHIOCARBAZATE Method of synthesis Method of analysis for active ingredient The same as in the case of nicotine dithiocarbazate.

NEONICOTINE MONOMETHYL-DITHIOCAR- BAMATE Method of synthesis Into a 4-necked fiask, there are introduced 84 g. 1.1 mol) of carbon bisulfide and 50 g. of water; 100 g. (30%, 1 mol) of monomethylamine is added dropwise from a tap funnel with agitation; after agitation of one hour since the completion of the addition, 540 g. of neonicotine solution (30%, 1 mol) is added dropwise and the solution turns to a brownish black, clear liquid. Upon cooling after agitating for one hour at 4045 C., excess of carbon bisultide is driven 01f at 4550 C. The pH is adjusted to 8.8- 9.0 with gaseous ammonia. 750 ml. of 35% product is obtained.

Method of analysis for active ingredient The same as in the case of nicotine monomethyl-dithiocarbamate.

NEONICOTINE DIETHYLENETRlAMINE-TRISDI- THIOCARBAMATE Method of synthesis Into a 4-necked flask, there are introduced 252 g. (3.3 mol) of carbon bisulfide and 50 g. of water; 206 g. (50%, 1 mol) of diethylenetriarnine is added dropwise from a tap funnel with agitation; after agitation of one hour since the completion of the addition, 1620 g. (30%, 3 mol) of neonicotine solution is added dropwise and the solutions turns to a brownish black, clear liquid. Upon cooling after agitating for one hour at 4045 C., excess of carbon bisulfide is driven off at 45 50 C. The pH is adjusted to 8.89.0 with gaseous ammonia, 2090 ml. of about 38% product is obtained.

Method of analysis for active ingredient The same as in the case of nicotine diethylenetriaminetrisdithiocarbamate.

NEONICOTINE PHENYLENE-BISDITHIOCAR- BAMATE Method of synthesis Into a 4-necked flask, there are introduced 168 g. (2.2 mol) of carbon bisulfide and 300 g. of water; 108 g. (1 mol) of solid phenylene diamine is added slowly with agitation; after agitation of one hour since the completion of the addition, 1080 g. of neonicotine solution (30%, 2 mol) is added dropwise and the solution turns to a brownish black, clear liquid. Upon cooling after agitating for one hour at 4045 C., excess of carbon bisulfide is driven off at 4550 C. The pH is adjusted to 8.8-9.0 with gaseous ammonia. 1630 ml. of about 35 product is obtained.

Method of analysis for active ingredient The same as in the case of nicotine phenylene-bisdithiocarbamate.

NEONICOTINE PHENYL-DITHIOCARBAMATE Method of synthesis Into a 4-necked flask, there are introduced 84 g. (1.1 mol) of carbon bisulfide and 100 g. of water; 93 g. (1 mol) of aniline is added dropwise with agitation; after agitation of one hour since the completion of the addition, 540 g. of neonicotine solution (30%, 1 mol) is added dropwise and the solution turns to a brownish black, clear liquid. Upon cooling after agitating for one hour at 40- 45 C., excess of carbon bisulfide is driven off at 45 50 C. The pH is adjusted to 8.89.0 with gaseous ammonia. 700 ml. of about 32% product is obtained.

Method of analysis The same as in the case of nicotine phenyl-dithiocarbamate.

NEONICOTINE PIPERAZiNE-BISDITHIOCAR- BAMATE Method of synthesis Into a 4-necked flask, there are introduced 167 g. (2.2 mol) of carbon bisulfide and 200 g. of water; 215 g. (40%, 1 mol) of piperazine solution is added dropwise from a tap funnel with agitation; after agitation of one hour since the completion of the addiition, 1080 g. of neonicotine solution (30%, 2 mol) is added dropwise and the solution turns to a brownish black, clear liquid. Upon cooling after agitating for one hour at 4045 C., excess of carbon bisulfide is driven off at 45 -50 C. The pH is adjusted to 8.8-9.0 with gaseous ammonia. 1640 ml. of about 34% product is obtained.

Method of analysis The same as in the case of nicotine piperazine-bisdithiocarbamate.

N ICOTINE DIETHYL-DITHIO CARBAMATE A1 ethod 0 f synthesis Into a 4-necked flask, there are introduced 84 g. 1.1 mol) of carbon disulfide and 250 g. of water; 123 g. (40%, 1 mol) of diethylamine is added dropwise from a tap funnel with agitation; after agitation of one hour since the completion of the addition, 170 g. of nicotine extract 1 mol) is added dropwise and the solution turns to a brownish black, clear liquid. Upon cooling after agitating for one hour at 40-45 C., excess of carbon bisultide is driven ofi at 45 50 C. The pH is adjusted to 8.8-9.0 with gaseous ammonia. 600 ml. of about 46% product is obtained.

Method of analysis 26111.) X Fr X3L0 Percent of active ingredient= sample (g.)

(b) Method of analysis for nicotine p0rtion.The same as in the case of nicotine ethylene-bisdithiocarbamate.

NICOTINE MONOETHYL-DITHIOCARBAMATE Into a 4-necked flask, there are introduced 84 g. 1.1 mol) ofcarbon bisulfide and 250 g. of water; 113 g. (40%, 1 mol) of monoethylamine is added dropwise from a tap funnel with agitation; after agitation of one hour smce the completion of the addition, g. of nicotine extract (95 1 mol) is added dropwise and the solution turns to a brownish black, clear liquid. Upon cooling after agitating for one hour at 40-45 C., excess of carbon bisulfide is driven oil at 45 50 C. The pH is adjusted to 8.89.0 with gaseous ammonia. 600 ml. of about 46% product is obtained.

Method of analysis 2am. XF X283 sample (g.)

([7) Method of analysis for nicotine portion-The same as in the case of nicotine ethylene-bisdithiocarbamate.

Percent of active ingredient= 1 NICOTINE MONOPROPYL-DITHIOCARBAMATE Method of synthesis Into a 4-necked flask, there are introduced 84 g. (1.1 mol) of carbon bisulfide and 250 g. of water; 148 g. (40%, 1 mol) of monopropylamine is added dropwise from a tap funnel with agitation; after agitation for one hour since the completion of the addition, 170 g. of nicotine extract (95%, 1 mol) is added dropwise and the solution turns to a brownish black, clear liquid. Upon cooling after agitating for one hour at 4045 C., excess of carbon bisulfide is expelled oh. at 45-50 C. The pH is adjusted to 8.89.0 with gaseous ammonia. 630 ml. of about 46% product is obtained.

Method of analysis (a) Method of analysis for active ingredient.The same as in the case of nicotine ethylene-bisdithiocarbamate, but, the calculation may be done as follows:

Percent of active ingredient sample (g) (b) Method of analysis for nicotine portion.The

same as in the case of nicotine ethylene-bisdithiocarbamate.

NICOTINE DIPROPYL-DITHIOCARBAMATE Method of synthesis Into a 4-necked flask, there are introduced 84 g. 1.1 mol) of carbon bisulfide and 300 g. of water; 253 g. (40%, 1 mol) of dipropylamine is added dropwise from a tap funnel with agitation; after agitation of one hour since the completion of the addition, 170 g. of nicotine extract (95%, 1 mol) is added dropwise and the solution turns to a brownish black, clear liquid. Upon cooling after agitating for one hour at 4045 C., excess of carbon bisulfide is driven off at 45-50 C. The pH is adjusted to 8.89.0 with gaseous ammonia. 780 ml. of 42% product is obtained.

Method of analysis (a) Method of analysis for active ingredient.The same as in the case of nicotine ethylene-bisdithiocarbamate, but, the calculation may be done as follows:

2(ml XFI X 33.9

Nicotine salt of ethylenebisdithiocarbamic acid was diluted with water to the solid matter by 1,000 times, 2,000 times, 5,000 times and 10,000 times. The eradicative activity upon Ophiobolus miyabeanus, Alternaria kikachiana, Xanthomona orygae, Xanthomona citri and Coli communis was tested. With even 10,000 times solution, 100% of such microorganisms were killed. For aphides, lace bugs, thrips, radish webworms, rice stem borers, rice leaf miner, peach leaf miner, cabbage sawfly, red spider, and pear sucker were completely killed by 2,000 times solution and the activity was observed in the case of 5,000 times solution. The nematicidal action upon imagines and eggs of nematodes is strong.

EXAMPLE 3 The prevention and expulsion test of diseases and insects for the crysanthemum was carried out by the use of nicotine salts of ethylenebisdithiocarbamic acid, dimethyl dithiocarbamic acid and dithiocarbazic acid. The 2,000 times diluted solution of the above-mentioned compounds was sprayed over plants. The result of test showed that 12 white rust and rust phillosticta spot could be controlled by the treatment, and that the damage by chrysanthemum aphid could be controlled at the same time.

EXAMPLE 4 The 2,000 times diluted solution of nicotine salt of ethylenebisdithiocarbamic acid was used for controlling tomato diseases. The prevention and expulsion of late blight and leaf mold were successed. Moreover, there could be completely controlled on the treated field the tomato disease caused by cucumber mosaic virus which appeared severely on the adjacent field.

EXAMPLE 5 The explusion test of soil-borne diseases, nematodes and other soil insects was carried out by means of injecting nicotine salt of monomethyldithiocarbamic acid into soil. In this test, 5 g. of the compound the water solution was injected into each one hole at intervals of 30 cm. and holes were closed after treatment and the treated soil was covered with plastic sheet. Among the cucumber, seedlings transplanted on the treated soil, there were no diseased plants affected by Fnsarium oxysporum, F. cucamerinum, Corticium rolfsii, and Pellicalaria filamentosa. And then damages of nematodes and Anomala spp. could be prevented. This treatment could also inhibit growth of weeds remarkably.

EXAMPLE 6 A series of tests for bacteriocidal, fungidical and insecticidal activities of the following compounds was carried out. Each compound was applied after diluted with water to give the solution in the listed concentration.

Nicotine ethylene-bisdithiocarbamate Nicotine dimethyl-dithiocarbamate Nicotine dithiocarbazate Nicotine diethylene-triamine-trisdithiocarbamate Nicotine phenylene-bisdithiocarbamate Nicotine phenyl-dithiocarbamate Nicotine piperazine-bisdithiocarbamate Nicotine monomethyl-dithiocarbamate Compound X. oryzae A. kikuchiana As to insecticidal activity, the chemicals of each selected concentration were compared with 800 times diluted aqueous solution of nicotine sulfate (containing 40% of free nicotine) added with 3 g. of sodium salts of fatty acids to 1 liter of diluted solution. The rate of killed insects were calculated after counting numbers of living green peach aphids on egg-plant leaves before and after the solutions sprayed with 3 cc. of alkyl-phenol-polyethylene oxide per 10 liter of them. The experimental results are indicated as follows:

tions only. In the cases of blends, where both of the ingredients were blended in 1:1 mol ratio, figures show the concentration in p.p.m. based on the total weights of Dilution Percent the preparations, and those in parentheses show the con- Compound 535 centration of total dithiocarbamate portions in p.p.m.

matter Xanthomo'nas Alttmarz'a 1:1 000 97. 5 Chemicals oryzae kikuchiana 1:1: 000 99. 5 11,000 98.5 irggg Nicotine ethylene-hisdithiocarbarnate- 2 0.3 25 (9.8)

15800 0 Ammonium ethylenerbisdithiocar- 111,000 9&5 bamate 2 (1.7) 26 (22. 4)

Nicotine monomethyl-dithiocarbamate 2 (0.8) 25 (9.9 Sodium monornethyl-dithiocarbamate." 3 (2.5) 25 (20.5)

Nicotine dimethy-dithiocarbamate 2 (0.8) 25 (10.6) EXAMPLE 7 Ammonium dimethyl-dithiocarbamate 2 (1.8) 22. s Bactericidal and insecticidal tests of the following corn- Nicotlne dithiocarbazate 5 (2.0) 45 (17.9) pound were run. All of them were employed by dissolving Sodmm mhmcarbazate 5 (4'2) 50 5) them in water and diluting them to indicated concentra- Nicotnildiethgleneitriamine- US it iocar ama e 9 3.6 80 32.3 tlons. Nconicotineused was a commercial roduct. 20 Ammonium diethylene mamme A. Runs wherein nicotine salt or neonicotine salt of trisdithiocarbamate 9 (7.7) so (73. 7) dlthlocarbamlc aclds was used alone: Niootin phenylene-bisdithiocarbamate 5 2.2 as (16.5) N in i-hyi n is i hi r m e *fininiffff ffifii??ifiitiliif 5 (4.4 40 3111) (2) Nicotine monomethyl-dithiocarbamate Nicotine h 1 1 ca b are 5 (9 5) 45 Q) poly-1 1o raml. .4. r dgmeihyl-dltmocarbamate Ammonium phenyl-dithiocarbamate.- 5 4.5 45 40.9 (4) Nicotine dithiocarbazate Nicofi i e (mm b t 3 1 3 3 I z1 1 (5) NlCOIlllfi diethylene-triamine-tr1sd1th1ocarbamate ffig f fli gi gg ggg gg e l 4 7) (6) Nicotine phenylene-bisdithiocarbamate bamate 4 (3-5) 35 (-6) (7) Nicotine phenyl-dithiocarbamate Neonicotine ethylenc-bisdithio- 30 (8) Nicotine prperazme-brsdithiocarbarnate wbamate 2 (0-3) 25 (9-8) Y Ammonium ethy1ene-b1sd1th1o- (9) I\eonicot1ne ethy1ene-b1sd1th1ocarbamate carbarnate 2 (1.7) 20 (22. 4) (l0) Neonicotine monomethyl-dithiocarbamate N e G 0mm monomethyl dithio (11) Neonicotine dimethyl-dithiocarbamate carhamnte s (0.8) 24 9.9 12 Neonicotine dithiocarbazate Sodium monornethyl-dithiocarbamate 3 (2.5) 25 (20.5) (13) Neonicotine diethylene-triamine-trisdithiocarbarnate Neonicotine dirnethyl-dithiocarbamate. 2 (0.9 25 10. 0) (l4) Neonicotine phenylene-bisdithiocarbamate Ammmmm dlmethyl'dlthmwbamate-" 2 (1'8) 26 (228) (15) Neonicotine phenyl-dithiocarbarnate Neqnicotine dithiocarbazate 5 (2.3) (17.9) (16) Neonicotine piperazine-bisdithiocarbamate sodmm dlthlocarbamte 5 (4'2) (4L5) B. Runs wherein mixtures of nicotine salts, neonicofifigifiifffiififififii; 6 (24) 60 (M2) tine salts and other salts of dithiocarbamic acids were gg fig q f i g i 8 (6 9) 85 7) used. 1 a l Neonicotine hen 1ene-bisclithio- (17) Nicotine ethylene -b1sd1th10carbamate+ammonium earbarnateflfli 5 2.2) 35 15.5 dimethyl-dithiocarbamate 3 3 313 phenylene-belithio- 5 (4 4) 40 (35 1) (18) Nicotine ethylene-bisdit'hiocarbamate+neonicotine 45 N eonicotine p11enyl-ditiiocarbarnate- 5 2.5) 45 22.9 dimethyl dithiocarbamate Ammonium phenyl-dithiocarbamat 5 54.5) 45 409) (19) Nicotine ethylene-b1sd1th1ccarbamate+mcot1ne phenylene-bisdithiocarbamate ggyggifggf i 3 (1 3) 34 (14 3) (20) Nicotine ethylene -bisdithiocarbamate+ammonium 5O o um p eny -b s o 4 (3.5) 5

p p f q q 'f Nicotine ethylene-bisdithiocarbamate (21) Nicotine dimethyl-dithiocarbamate+s0d1um phenyl- P g dimethyl-dithio- 2 0) car ama e l. 20 9.8 eneblsdllghloFarbamate Ammonium bisdithiocar- (22) Neonicotrne monomethyl-drthiocarbamate+sodium bamfite u 2 26 Phenyhdflhwcarbamate Nicotine ethylenebisdithiocarbarnate r plus neomcotme ethylene-b1sd1th1o- For control tests, the following compounds were used. carbamate 2 (0.8) 20 (8.1)

Ammonium ethylene-bisdithiocar- (23) Ammonium ethylene-bisdithiocarbamate barnate 2 (1.7) 26 (22.4) m f flunmyldlthwcarb amate Nicotine etliylene-bisdithiocarbarnate (25) SOdllllTi dithiocarbazate plus nicotine phenylene-bisdithio- (2e) Ammonium diethyi-tr iamine-trisdithiocarbamate fggjj figfigggg g gig ggjggg gg 2 (0'8) 26 9) (2/) Ammonium phenyl-dithrocarbamate bamate 2 26 (28) Ammonium prperazme-b1sd1th1ocarbamate Nicotine ethylene-bi sdithiocarbarnate (29) Sodium monomethyhdithlocarbamate g g gg plperazmeblsdlthw- 2 1 I m (30) Ammomum phenylene-b1sd1th1ocarbamate Alimontmm ethylenefbisdithiocar. 1) 20 (u 0) ama e 2 1. 2 .4 Against Alranarza kzkuchzana, diluted solution of van- 7) 26 2 a Nicotine dimethyl-dithiocarbamate ous concentration were prepared and slide glasses were plus Sodium phenylene bisdithio used. Germination rates of spores were measured and car-brunette 2 (1.3) 20 (12.9) minimum concentration to inhibit 95% of spores were Ammomum dlmethyl'dthmcarbamate" 2 (1'8) 26 (22-8) determined. In the case of Xanthomonas oryzae, culture Neon icotine monomethyldithiocarbamedia containing those chemicals in various concentra- P f j i 3 (1 8) 2O (12 O) tions were prepared and inoculated with the strain to Sodium monomethvldithiowrbamine--- 3 25 determine the minimum concentration to inhibit the growth. The results are as follows. Figures in parentheses As will be seen from the above table, the activities of show in p.p.m. the concentrations of dithiocarbamate por- 7 dithiocarbamic acids are highly enhanced by rendering 15 them to nicotine salts or neonicotine salts. For instance, in the case of ethylene-bisdithiocarbamic acid, they have the sameeifectiveness in one half amount of ammonium type salts by employing them in nicotine salt or neonicotimes aqueous solution of aqueous nicotine sulfate solution or aqueous neonicotine sulfate solution (containing 40% of free nicotine or neonicotine) thereto. For the purpose of control tests, 600-times solution of aqueous nicotine sulfate as prepared, were employed. Tests were conducted against Myzus persicae Sulzer (apterous form) infesting egg plants, by measuring the number of the insects alive before and after spraying to determine the mortality. The results are shown in the following table. In this table, concentrations are shown in dilutions to whole solids of nicotine dithiocarbamates or neonicotine dithiocarbamates, and also in dilutions to nicotine portons or neonicotine portions, the latter being shown in parentheses. In the cases of blends, as in the case of bactericidal tests, which were composed of ingredients in 1:1 mol ratio, figures indicated show dilutions to whole solids and also to nicotine portions of neonicotine portions.

Dilution to Whole solids Chemicals (dilution to Mortality nicotine, neonicotine portion) Nicotine ethylene bis'dithiocarbamate 121200 (1:1978) 97. Nicotine monomethyl-dithiocarbarnate. 1:1200 (1:1986) 09. 5 Nicotine dimethyl-dithiocarbamate 121200 (1:2089) 96.7 Nicotine dithiocarbazate 121200 (121993) 98. 5 Nicotine diethylene-triaminetrisd carbamate 121200 (122010) 97. 5 Nicotine phenylene-bisdithiocarb 1-1000 (1:1796) 06. 5 Nicotine phenyl-dithiocarbamate 1 1000 (112137) 97.0 Nicotine piperazine-bisdithiocarbama 1 1200 (122074) 98. 5 Neonicotine ethylene-bisdithiocarbamate.. 1 1200 (1:1978) 97.2 Neonicotine mcnomethyl-dithiocarbar mate 121200 (1:1986) 99. 2 Neonicotine ethyl-dithiocarbamate 121200 (1:2089) 96. 5 .Neonicotine dithiocarbazate 121200 (1:1993) 98.1 .Ne'onicotine diethylenetriaminetrisdithiocarbamate 111200 (112010) 97. 2 vNeonicotine phenylene-bisdithiocarbamate-- 1. 121000 (1:1796) 96. 5 Neonicotine phenyl-dlthiocarbamate 1:1000 (122137) 97.3 Neonicotine piperazlne-bisdithiocarbamate 121200 (122074) 97. 9 Nicotine ethylene-bisdithiocarbmate plus ammonium dimethyldithiocarbamate 1:600 (1:2 .89) 93. 8 Nicotine ethylenebisdithiocarbamate plus ueonicotine dimethyl-dithiocarbamate 1:800 (1 :2015) 97. 1 Nicotine ethylene-bisdithiocarbamate plus nicotine phenylenebisdithiocarbamate 1:600 (1:2057) 97. 3 Nicotine ethylene-bisdithiocarbarnate plus ammonium piperazine bisdithiocarbamate 1:800 (121090) 08.1 Nicotine dimethyl-dithiocarbamate plus sodium phenyleuebisdithiocarbamate 1:600 (122170) 97. 8 Neonicotine monornethyl-dithiocarbamate plus sodium phenyl-dithiocarba- V mate 1:700 (1:1983) 99. 4 Nicotine sulfate plus sodium soap. 1:800 (122000) 92. 5 Nicotine sulfate 1:600 (111500) 89. 5 Neonicotine sulfate 1:600 (1:1500) 86.5

As will be seen from the above table, nicotine and neonicotine dithiocarbamates and blends composed of more than two thereof exhibit very high insecticidal activities vwhen they are diluted and sprayed as diluted, and the activities are farmore than those of nicotine and neonicotine sulfate, sprayed as diluted. They are more than equal to those of nicotine sulfate added with sodium soap. This fact shows that they are very hi h in practical utility.

1 6 EXAMPLE 8 50 g. of water is added to g. of 45% nicotine ethylene-bisdithiocarbamate solution which has high viscosity. By the addition of 5 g. of ethyleneglycol to the solution, a lower viscous solution is obtained, then the formulated solution becomes easily dealed with as a pesticide.

EXAMPLE 9 EXAMPLE 10 15 g. of nicotine dirnethyl-dithiocarbamate which is dried under vacuum (40 G, 5-10 mm. Hg) is mixed with talc and the total weight is adjusted to .100 g. Thus, 15% wettable powder of nicotine dimethyl-dithiocarbamate is obtained.

We claim:

1. A nicotinic alkaloid salt of (a) an acid selected from the group consisting of polydithioca-rbamic acid, N- dialkyldithiocarba-mic acid, M-mono-alkyl dithiocarbamic acid, N-mono-phenyl dithiocarbamic acid, dithio-car'oazic acid and mixtures thereof, wherein each alkyl group has 1 to 3 carbon atoms, with (b) a nicotinic alkaloid selected from the group consisting of nicotine, neonicotine and anabasine.

2. A pesticidal composition comprising a'ca-rrier, and an effective amount of at least one nicotinic alkaloid salt of (a) an acid selected from the group consisting of poly dithiocarbamic acid, N-dialkyl dithiocarbamic acid, M-mono-alkyl dithiocarbamic acid, N-rnono-phenyl dithiocarbarnic acid, dithiocarbazic acid and mixtures thereof, wherein each alkyl group has 1 to 3 carbon atoms, with (b) a nicotinic alkaloid selected from the group consisting of nicotine, neonicotine and anabasine.

3. A pesticidal composition which comprises as an active ingredient, at least one nicotinic alkaloid salt of (a) an acid selected from the group consisting of poly dithiocarbamic acid, N-dialkyl dithiocarbamic acid, N-

mono-alkyl dithiocarbarnic acid, N-mono-phenyl dithio-,

carbamic acid, dithiocarbazic acid and mixtures thereof, wherein each alkyl group has 1 to 3 carbon atoms, with (b) a nicotinic alkaloid selected from the group consisting of nicotine, neonicotine and anabasine, and an organic solvent selected from the group consisting of methanol,

ethanol, propanol, isopropanol, butanol, isobutanol, amyl-- alcohol, ethyleneglycol, glycerine, acetone, methyl ethyl ketone, dimcthyl-formamide and dimethyl-sulfoxide.

4. A pesticidal composition which comprises as an active ingredient, at least one nicotinic alkaloid salt of (a) an acid selected from the group consisting of polydithiocarbamic acid, N-dialkyldithiocarbamic acid, N-

mono-alkyl dithiocarbarnic acid, N-mono-phenyl dithiocarbamic acid, dithiocarbazic acid and mixtures thereof, wherein each alkyl group has 1 to 3 carbon atoms, with (b) a nicotinic alkaloid selected from the group consisting of nicotine, neonicotine and anabasine, and a solid carrier selected from the group consisting of talc, bentonite and clay.

5. A nicotinic alkaloid salt selected from the group consisting of nicotine ethylene-bisdithiocarb'amate, niconeonicotine phenyl-dithiocarbamate and neonicotine piperazine-bisdithiocarbamate.

6. A method for controlling bacteria, fungi, insects and nematodes, which comprises contacting the'l'pest to be controlled with an effective amount of at least one nicotinic alkaloid salt of (a) an acid selected from the group consisting of polydithiocarbamic acid, N-dialkyldithiocarbarnic acid, M-mono-alkyl dithiocarbamic acid, N- mono-phenyl dithiocarbamic acid, dithiocarbazic acid and mixture thereof, wherein each alkyl group has'l to 3 carbon atoms, with (b) a nicotinic alkaloid selected from the group consisting of nicotine, neouicotine and anabasine.

References Cited UNITED STATES PATENTS Re. 22,750 4/1946 Tisdale et a1. 167-22 18 2,077,960 4/1937 SibIeS 260-291 X 2,411,253 11/1946 Flenner et a1. 16722 2,463,666 3/1949 Woodward et al 260-291 2,466,788 4/ 1949 Woodward et al l67 34 2,973,297 2/ 1961 Bakkeren et a1. 167-22 OTHER REFERENCES Levi: Gazz. Chem. Italiana 61:803-814 1931 Chabrier et al.: Bull. Societe Chimique de France, pages D-Sl to D 65, January-June 1950.

LEWIS GOTTS, Primary Examiner.

15 s. K. ROSE, Assistant Examiner. 

